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We present electron spin resonance data of Ti$^{3+}$ (3$d^1$) ions in singlecrystals of the novel layered quantum spin magnet TiOCl. The analysis of the gtensor yields direct evidence that the d_{xy} orbital from the t_{2g} set ispredominantly occupied and owing to the occurrence of orbital order a linearspin chain forms along the crystallographic b axis. This result corroboratesrecent theoretical LDA+U calculations of the band structure. The temperaturedependence of the parameters of the resonance signal suggests a strong couplingbetween spin and lattice degrees of freedom and gives evidence for a transitionto a nonmagnetic ground state at 67 K.Comment: revised version, accepted for publication in Phys. Rev. B, Rapid Com

Orbital order in the low-dimensional quantum spin system TiOCl probed by ESR